Propylene polymers compositions

ABSTRACT

A propylene composition comprising (percent by weight):
         A) 60%-95%, of a crystalline propylene copolymer containing from 2.0% to 10.0% of ethylene derived units having a melting point ranging from 148° C. to 160° C.; wherein the melting temperature Tm is measured by DSC on the as-reactor polymer;   B) 40%-5%, of a copolymer of ethylene containing from 70% to 85%, of ethylene derived units intrinsic viscosity ranging from 0.8 to 3 dl/g.

This application is the U.S. national phase of International ApplicationPCT/EP2010/064736, filed Oct. 4, 2010, claiming priority to EuropeanApplication 09172881.6 filed Oct. 13, 2009, and the benefit under 35U.S.C. 119(e) of U.S. Provisional Application No. 61/279,591, filed Oct.23, 2009; the disclosures of International ApplicationPCT/EP2010/064736, European Application 09172881.6 and U.S. ProvisionalApplication No. 61/279,591, each as filed, are incorporated herein byreference.

The present invention relates to a propylene polymer composition havingan optimum balance of properties in particular improved impact strengthand excellent optical properties. As is known, the isotacticpolypropylene is endowed with an exceptional combination of excellentproperties which render it suitable for a very great number of uses. Inorder to improve said properties into the propylene stereoregularhomopolymerization process have been introduced one or morecopolymerization steps or one or more monomer have been introduced inthe homopolymer matrix.

WO 2006/037705 relates to an olefin polymer composition comprising (byweight, unless otherwise specified):

A) 60-85%, preferably 65-80%, more preferably 65-75%, of a crystallinepropylene homopolymer or a crystalline copolymer of propylene containing3% or less of ethylene or C₄-C₁₀ a-olefin(s) or of combinations thereof,said homopolymer or copolymer having a Polydispersity Index (P.I.) valueof from 4.5-6, preferably 4.5-5.5, and a content of isotactic pentads(mmmm), measured by ¹³C NMR on the fraction insoluble in xylene at 25°C., higher than 96%, preferably higher than 98%;

B) 15-40%, preferably 20-35%, more preferably 25-35%, of a partiallyamorphous copolymer of ethylene containing from 35% to 70%, preferablyfrom 40 to 55%, of propylene or C₄-C₁₀ a-olefin(s) or of combinationsthereof, and optionally minor proportions of a diene. The olefin polymercomposition exhibits a value of elongation at break ranging from 150 to600%, preferably 200-500%, according to ISO method 527.

EP 603 723 relates to a polypropylene compositions comprising:

A) from 70 to 98 parts by weight of a crystalline propylene homopolymer,or a crystalline random copolymer of propylene with ethylene and/orC₄-C₁₀ alpha-olefins, containing from 0.5 to 10% by weight of ethyleneand/or a-olefins (Fraction A); and

B) from 2 to 30 parts by weight of elastomeric copolymer of ethylenewith one or more C₄-C₁₀ a-olefins, containing from 60 to 85% by weightof ethylene, and partially soluble in xylene at 25° C. (Fraction B);

Wherein said composition has an intrinsic viscosity value intetrahydronaphthalene at 135° C. of the fraction soluble in xylene at25° C. ranging from 0.8 to 1.1 dl/g.

The applicant found that the properties of these compositions,especially in terms of impact and transparency, can be improved by usinga polypropylene matrix (polymer A) having a particular balance betweenmelting point and ethylene content.

The object of the present invention is a propylene compositioncomprising (percent by weight):

A) 60%-95%, preferably 65%-90%, more preferably 70%-88%, of a propylenecopolymer containing from 2.0% to 10.0% preferably from 3.0% to 6.0%more preferably from 3.1% to 6.0% of ethylene derived units having amelting temperature Tm ranging from 148° C. to 160° C. preferably from149° C. to 160° C., preferably from 149° C. to 158° C., more preferablyfrom 150° C. to 156° C.;

the Tm values characterizing the propylene polymers of the inventionhave to be measured on the “as-reactor polymer”, i.e. on the polymer assuch without adding any additive or filler, in particular without addingnucleating agents.

B) 5%-40%, preferably 10%-35%, more preferably 12%-30% of a copolymer ofethylene with from 60% to 85%, preferably from 70% to 85%, morepreferably from 71% to 82%; even more preferably from 71% to 81% ofethylene derived units, and having an intrinsic viscosity ranging from0.8 to 3 dl/g preferably from 0.9 to 2.5 dl/g more preferably from 1 to2 dl/g. From the above definitions it is evident that the term“copolymer” includes polymers containing only two kinds of comonomers.

Preferably in the propylene copolymer A) the ethylene content (C2) andthe melting point (Tm) fulfil the following relationship:Tm>C2*−0.56+150.5preferably the relationship isTm>C2*−0.56+150.8Even more preferably the relationship is:Tm>C2*−0.56+151.2

Other preferred features for the compositions of the present inventionare:

crystallization temperature Tc ranging from 95° C. to 120° C.;

MFR L (Melt Flow Rate according to ASTM 1238, condition L, i.e. 230° C.and 2.16 kg load) from 0.5 to 50 10 g/10 min, in particular from 9 to 30g/10 min.; more preferably more preferably from 15 to 25 10 g/10 min;

-   -   Intrinsic Viscosity [I.V.] of the fraction (of the overall        composition) soluble in xylene at room temperature: from 1.2 to        4.5, more preferably from 1.2. to 3 dl/g; even more preferably        from 1.2 to 2 dl/g;

Moreover, the compositions of the present invention preferably areendowed with some or all these properties:

-   -   Haze measured on 1 mm plaques lower than 30%; preferably lower        than 25%; even more preferably lower than 20%;    -   Izod impact strength measured at 23° C. higher than 4 KJ/m²;    -   ductile brittle temperature lower than +5° C., preferably lower        than −3° C., more preferably lower than −6° C., even more        preferably lower than −14° C., even more preferably lower than        −19° C.

The propylene polymer compositions of the present invention can beprepared by sequential polymerization in at least two stages, with eachsubsequent polymerization stage being conducted in the presence of thepolymeric material formed in the immediately preceding polymerizationreaction, wherein the copolymer (A) is normally prepared in at least onefirst polymerization stage and the copolymer (B) is normally prepared inat least one second polymerization stage.

Preferably, each polymerization stage is carried out in presence of ahighly stereospecific heterogeneous Ziegler-Natta catalyst. TheZiegler-Natta catalysts suitable for producing the propylene polymercompositions of the invention comprise a solid catalyst componentcomprising at least one titanium compound having at least onetitanium-halogen bond and at least an electron-donor compound (internaldonor), both supported on magnesium chloride. The Ziegler-Nattacatalysts systems further comprise an organo-aluminum compound asessential cocatalyst and optionally an external electron-donor compound.

Suitable catalysts systems are described in the European patentsEP45977, EP361494, EP728769, EP 1272533 and in the international patentapplication W000163261.

Preferably, the solid catalyst component comprises Mg, Ti, halogen andan electron donor selected from succinates of formula (I):

wherein the radicals R¹ and R², equal to or different from each other,are a C₁-C₂₀ linear or branched alkyl, alkenyl, cycloalkyl, aryl,arylalkyl or alkylaryl group, optionally containing heteroatomsbelonging to groups 15-17 of the periodic table; the radicals R³ to R⁶equal to or different from each other, are hydrogen or a C₁-C₂ linear orbranched alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group,optionally containing heteroatoms, and the radicals R³ to R⁶ which arejoined to the same carbon atom can be linked together to form a cycle.

R¹ and R² are preferably C₁-C₈ alkyl, cycloalkyl, aryl, arylalkyl andalkylaryl groups.

Particularly preferred are the compounds in which R¹ and R² are selectedfrom primary alkyls and in particular branched primary alkyls. Examplesof suitable R¹ and R² groups are methyl, ethyl, n-propyl, n-butyl,isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl,isobutyl, and neopentyl.

One of the preferred groups of compounds described by the formula (I) isthat in which R³ to R⁵ are hydrogen and R⁶ is a branched alkyl,cycloalkyl, aryl, arylalkyl and alkylaryl radical having from 3 to 10carbon atoms. Another preferred group of compounds within those offormula (I) is that in which at least two radicals from R³ to R⁶ aredifferent from hydrogen and are selected from C₁-C₂₀ linear or branchedalkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl group,optionally containing heteroatoms belonging to groups.

Particularly preferred are the compounds in which the two radicalsdifferent from hydrogen are linked to the same carbon atom. Furthermore,also the compounds in which at least two radicals different fromhydrogen are linked to different carbon atoms, that is R³ and R⁵ or R⁴and R⁶ are particularly preferred.

According to a preferred method, the solid catalyst component can beprepared by reacting a titanium compound of formula Ti(OR)_(n−y)X_(y)where n is the valence of titanium and y is a number between 1 and n,preferably TiC4, with a magnesium chloride deriving from an adduct offormula MgCl₂·pROH, where p is a number between 0.1 and 6, preferablyfrom 2 to 3.5, and R is a hydrocarbon radical having 1-18 carbon atoms.The adduct can be suitably prepared in spherical form by mixing alcoholand magnesium chloride in the presence of an inert hydrocarbonimmiscible with the adduct, operating under stirring conditions at themelting temperature of the adduct (100-130° C.). Then, the emulsion isquickly quenched, thereby causing the solidification of the adduct inform of spherical particles. Examples of spherical adducts preparedaccording to this procedure are described in U.S. Pat. No. 4,399,054 andU.S. Pat. No. 4,469,648. The so obtained adduct can be directly reactedwith the Ti compound or it can be previously subjected to thermalcontrolled dealcoholation (80-130° C.) so as to obtain an adduct inwhich the number of moles of alcohol is generally lower than 3,preferably between 0.1 and 2.5. The reaction with the Ti compound can becarried out by suspending the adduct (dealcoholated or as such) in coldTiCl₄ (generally 0° C.); the mixture is heated up to 80-130° C. and keptat this temperature for 0.5-2 hours. The treatment with Tic4 can becarried out one or more times. The internal donor can be added duringthe treatment with TiCl₄ and the treatment with the electron donorcompound can be repeated one or more times. Generally, the succinate offormula (I) is used in molar ratio with respect to the MgC12 of from0.01 to 1 preferably from 0.05 to 0.5. The preparation of catalystcomponents in spherical form is described for example in European patentapplication EP-A-395083 and in the International patent applicationW098144001. The solid catalyst components obtained according to theabove method show a surface area (by B.E.T. method) generally between 20and 500 m21g and preferably between 50 and 400 m21g, and a totalporosity (by B.E.T. method) higher than 0.2 cm31g preferably between 0.2and 0.6 cm31g. The porosity (Hg method) due to pores with radius up to10.000 A generally ranges from 0.3 to 1.5 cm31g, preferably from 0.45 to1 cm31g.

The organo-aluminum compound is preferably an alkyl-Al selected from thetrialkyl aluminum compounds such as for example triethylaluminum,triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum. It is also possible to use mixtures oftrialkylaluminum's with alkylaluminum halides, alkylaluminum hydrides oralkylaluminum sesquichlorides such as AlEt₂Cl and Al₂Et₃Cl₃.

Preferred external electron-donor compounds include silicon compounds,ethers, esters such as ethyl 4-ethoxybenzoate, amines, heterocycliccompounds and particularly 2,2,6,6-tetramethyl piperidine, ketones andthe 1,3-diethers. Another class of preferred external donor compounds isthat of silicon compounds of formula R_(a) ⁵R_(b) ⁶Si(OR⁷)_(c) where aand b are integer from 0 to 2, c is an integer from 1 to 3 and the sum(a+b+c) is 4; R⁵, R⁶, and R⁷, are alkyl, cycloalkyl or aryl radicalswith 1-18 carbon atoms optionally containing heteroatoms. Particularlypreferred are methylcyclohexyldimethoxysilane, diphenyldimethoxysilane,methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane,2-ethylpiperidinyl-2-t-butyldimethoxysilane and 1,1,1,trifluoropropyl-2-ethylpiperidinyl-dimethoxysilane and 1,1,1,trifluoropropyl-metildimethoxysilane. The external electron donorcompound is used in such an amount to give a molar ratio between theorgano-aluminum compound and said electron donor compound of from 0.1 to500.

The propylene copolymer A is obtainable by polymerizing propylene andethylene by a gas-phase polymerization process carried out in at leasttwo interconnected polymerization zones, the process comprising feedingpropylene and the at least one linear or branched alpha-olefin having 2to 8 carbon atoms other than propylene to said polymerization zones inthe presence of a highly stereospecific heterogeneous Ziegler-Nattacatalyst system under reaction conditions and collecting the polymerproduct from said polymerization zones, in which process the growingpolymer particles flow upward through one of said polymerization zones(riser) under fast fluidization conditions, leave said riser and enteranother polymerization zone (downcomer) through which they flow downwardunder the action of gravity, leave said downcomer and are reintroducedinto the riser, thus establishing a circulation of polymer between theriser and the downcomer, whereby means are provided which are capable oftotally or partially preventing the gas mixture present in the riserfrom entering the downcomer and a gas and/or liquid mixture having acomposition different from the gas mixture present in the riser isintroduced into the downcomer, the process being further characterizedin that:

the monomer feed ratio C₂ ⁻(C₂ ⁻+C₃ ⁻) to the riser ranges from 0.020 to1.000 mol/mol.

In the polymerization process, the growing polymer flows through a firstpolymerization zone, represented by the riser, under fast fluidizationconditions. The two polymerization zones are appropriatelyinterconnected. The growing polymer and the gaseous mixture leaving theriser are conveyed to a separation zone whereby the gaseous mixture isseparated from the growing polymer. From the separation zone, thegrowing polymer enters the second polymerization zone, represented bythe downcomer, where the growing polymer flows in a densified form underthe action of gravity. The growing polymer particles leave said secondpolymerization zone and are reintroduced into said first polymerizationzone, thus establishing a circulation of polymer between the twopolymerization zones. The material balance is maintained by feeding inmonomers and catalysts and discharging polymer powder. Generally, theconditions of fast fluidization in the first polymerization zone isestablished by feeding the monomers gas mixture below the point ofreintroduction of the growing polymer into said first polymerizationzone. The velocity of the transport gas injected into the riser has tobe higher than the transport velocity under the operating conditions,and depends on the gas density and the particle size distribution of thesolid. It is preferably comprised between 0.5 and 15 m/s, morepreferably between 0.8 and 5 m/s. Generally, the various catalystcomponents are fed to the riser through a line that is preferably placedin the lower part of the riser. However, they can be fed at any otherpoint of the riser, as well as at any point of the downcomer or of theinterconnecting sections. The gas mixture that is separated from thecirculating solid in the separation zone must be totally or partiallyprevented to enter the downcomer. This can be achieved by feeding a gasand/or liquid into the downcomer through a line placed at a suitablepoint of said downcomer, preferably in the upper part thereof, throughone or more introduction lines. The gas and/or liquid mixture to be fedinto the downcomer should have an appropriate composition, differentfrom that of the gas mixture present in the riser. The said gas and/orliquid mixture partially or totally replaces the gas mixture entrainedwith the polymer particles entering the downcomer. The flow rate of thisgas feed can be regulated so that a flow of gas counter-current to theflow of polymer particles is originated in the downcomer, particularlyat the top thereof, thus acting as a barrier to the gas mixture comingfrom the riser which is entrained among the polymer particles. Accordingto a particularly preferred embodiment, the gas and/or liquid mixture ofdifferent composition to be fed into the downcomer is fed in partiallyor totally liquefied form. More preferably, said gas and/or liquidmixture consists of liquefied propylene.

Optionally, one or more inert gases, such as nitrogen or an aliphatichydrocarbon, are maintained in the polymerization zones, in suchquantities that the sum of the partial pressures of the inert gases ispreferably between 5 and 80% of the total pressure of the gases. Theoperating parameters such as, for example, the temperature are thosethat are usual in gas-phase olefin polymerization processes, for examplebetween 50° C. and 120° C., preferably from 70° C. to 90° C. The processcan be carried out under operating pressure of between 0,5 and 10 MPa,preferably between 1.5 and 6 MPa. The polymerization apparatus suitablefor carrying out the process is described in details in theInternational Patent Application WO00/02929, in particular in FIG. 4.The molecular weight distribution of the growing polymers can beconveniently tailored by metering customary molecular weight regulators,particularly hydrogen, in different proportion into at least onepolymerization zone, preferably into the riser. The process for theproduction of copolymer (A) is described in WO 2008/012144.

Polymer (B) is obtained by a polymerization in a gas phase in thepresence of copolymer (A) without intermediate stages except for thepartial degassing of the monomers. The reaction time, temperature andpressure of the polymerization steps are not critical, however thetemperature for the preparation of fraction (A) and (B), that can be thesame or different, is usually from 50° C. to 120° C. The polymerizationpressure preferably ranges from 0.5 to 12 MPa if the polymerization iscarried out in gas-phase. The catalytic system can be pre-contacted(pre-polymerized) with small amounts of olefins. The molecular weight ofthe propylene polymer composition is regulated by using knownregulators, such as hydrogen.

In the second stage of the particularly preferred polymerizationprocess, the ethylene/propylene copolymer (B) is produced in aconventional fluidized-bed gas-phase reactor in the presence of thepolymeric material and the catalyst system coming from the precedingpolymerization step. The polymerization mixture is discharged from thedowncomer to a gas-solid separator, and subsequently fed to thefluidized-bed gas-phase reactor operating under conventional conditionsof temperature and pressure.

The propylene polymer compositions of the present invention can also beobtained by separately preparing the said copolymers (A) and (B),operating with the same catalysts and substantially under the samepolymerization conditions as previously illustrated and subsequentlymechanically blending said copolymers in the molten state usingconventional mixing apparatuses, like twin-screw extruders.

The propylene polymer compositions of the present invention may furthercomprise additives commonly employed in the polyolefin field, such asantioxidants, light stabilizers, nucleating agents, antiacids, colorantsand fillers.

The main application of the propylene polymer compositions of theinvention is the production of molded articles, particularlyinjection-molded items. The injection-molded articles comprising thepropylene polymer compositions of the invention have good flexibilityand good impact properties and are also endowed with good transparency.

The following examples are given to illustrate and not to limit thepresent invention.

EXAMPLES

The data of the propylene polymer materials were obtained according tothe following methods:

Xylene-Soluble Faction

2.5 g of polymer and 250 rnL of o-xylene are introduced in a glass flaskequipped with a refrigerator and a magnetical stirrer. The temperatureis raised in 30 minutes up to the boiling pint of the solvent. The soobtained solution is then kept under reflux and stirring for further 30minutes. The closed flask is then kept for 30 minutes in a bath of iceand water and in thermostatic water bath at 25 OC for 30 minutes aswell. The solid thus obtained is filtered on quick filtering paper andthe filtered liquid is divided into two 100 ml aliquots. One 100 mlaliquots of the filtered liquid is poured in a previously weighedaluminum container, which is heated on a heating plate under nitrogenflow, to remove the solvent by evaporation. The container is then kepton an oven at 80° C. under vacuum until constant weight is obtained. Theresidue is weighed to determine the percentage of xylene-solublepolymer.

Ethylene (C2) Content

By IR spectroscopy.

The comonomer content of the Component B is determined on theprecipitated “amorphous” fraction of the polymer. The precipitated“amorphous” fraction is obtained as follows: to one 100 ml aliquot ofthe filtered liquid obtained as described above (procedure for theXylene-soluble faction) 200 ml of acetone are added under vigorousstirring. Precipitation must be complete as evidenced by a clearsolid-solution separation. The solid thus obtained is filtered on atared metallic screen and dried in a vacuum oven at 70° C. until aconstant weight is reached.

Molar Ratio Of Feed Gasses

Determined by gas-chromatography

Melt flow rate (MFR)

Determined according to ISO 1133 (230° C., 2.16 Kg)

Intrinsic Viscosity

Determined in tetrahydronaphthalene at 135° C.

Number Average Molecular Weight and Weight Average Molecular Weight

The determination of the molecular weights and the molecular weightdistribution Mw/Mn was carried out by gel permeation chromatography(GPC) at 145° C. in 1,2,4-trichlorobenzene using a GPC apparatus model150C from Waters. The data were evaluated by means of the Win-GPCsoftware from HS-Entwicklungsgesellschaft fir wissenschaftliche Hard-and Software GmbH, Ober-Hilbersheim. The columns were calibrated bymeans of polypropylene standards having molecular weights from 100 to107 g/mol.

Flexural Modulus

Determined according to ISO 178

Stress at Yield and at Break

Determined according to ISO 527

Elongation at Yield and Break

Determined according to ISO 527

IZOD Impact Strength

Determined according to ISO 18011A

Ductile/Brittle Transition Temperature (D/B)

According to this method, the bi-axial impact resistance is determinedthrough impact with an automatic, computerized striking hammer.

The circular test specimens are obtained by cutting with circular handpunch (38 mm diameter). They are conditioned for at least 12 hours at23° C. and 50 RH and then placed in a thermostatic bath at testingtemperature for 1 hour. The force-time curve is detected during impactof a striking hammer (5.3 kg, hemispheric punch with a ½″ diameter) on acircular specimen resting on a ring support. The machine used is a CEAST67581000 type model no. 2.

D/B transition temperature is the temperature at which 50% of thesamples undergoes fragile break when submitted to the above-mentionedimpact test. The plaques for DB measurements, having dimensions of127×127×1.5 mm are prepared according to the following method.

The injection press is a Negri Bossi™ type (NB 90) with a clamping forceof 90 tons. The mould is a rectangular plaque (127×127×1.5 mm).

The main process parameters are reported below:

Back pressure (bar): 20

Injection time (s): 3

Maximum Injection pressure (MPa): 14

Hydraulic injection pressure (MPa): 6−3

First holding hydraulic pressure (MPa): 4±2

First holding time (s): 3

Second holding hydraulic pressure (MPa): 3±2

Second holding time (s): 7

Cooling time (s): 20

Mould temperature (° C.): 60

The melt temperature is between 220 and 280° C.

Haze (on 1 mm Plaque)

According to the method used, 5×5 cm specimens are cut molded plaques of1 mm thick and the haze value is measured using a Gardner photometricunit connected to a Hazemeter type UX-10 or an equivalent instrumenthaving G.E. 1209 light source with filter “C”. Reference samples ofknown haze are used for calibrating the instrument. The plaques to betested are produced according to the following method.

75×75×1 mm plaques are molded with a GBF Plastiniector G235190 InjectionMolding Machine, 90 tons under the following processing conditions:

Screw rotation speed: 120 rpm

Back pressure: 10 bar

Melt temperature: 260° C.

Injection time: 5 sec

Switch to hold pressure: 50 bar

First stage hold pressure: 30 bar

Second stage pressure: 20 bar

Hold pressure profile: First stage 5 sec

Second stage 10 sec

Cooling time: 20 sec

Mold water temperature: 40° C.

Hexane Extractable

The hexane extractable fraction is determined according to modified FDAmethod (federal registration, title 21, Chapter 1, part 177, section1520, s. Annex B) on polymer formed into 100 ym thick items.

Melting Temperature, Melting Enthalpy and Crystallization Temperature

Determined by differential scanning calorimetry (DSC). weighting 6±1 mg,is heated to 220±1° C. at a rate of 20° C./min and kept at 220±1° C. for2 minutes in nitrogen stream and it is thereafter cooled at a rate of20° C./min to 40±2° C., thereby kept at this temperature for 2 min tocrystallise the sample. Then, the sample is again fused at a temperaturerise rate of 20° C./min up to 220° C.±1. The melting scan is recorded, athermogram is obtained, and, from this, melting temperatures andcrystallization temperatures are read.

Example 1 Polymerization Equipment

The propylene polymer compositions of the example were prepared in atwo-step polymerization process, wherein the copolymer (A) was preparedin the first polymerization step by feeing the monomers and the catalystsystem to a gas-phase polymerization reactor comprising twointerconnected polymerization zones, a riser and a downcomer, asdescribed in the European Patent EP782587. The polymerization mixturewas discharged from said reactor, conveyed to a gas-solid separator andthe polymerized material was sent into a conventional gas-phasefluidized-bed reactor where the ethylene/propylene copolymer (B) wasproduced. The operative conditions are indicated in Table 1.

Example 1

The solid catalyst used to prepare the propylene polymers was preparedaccording to the Example 5, lines 48-55 of the European Patent EP728769.Triethylaluminium (TEAL) was used as co-catalyst anddicyclopentyldimethoxysilane as external donor. The propylene polymerswere prepared by feeding the monomers and the catalyst system to thepolymerization equipment indicated above. The polymer powders weresubjected to a steam treatment to remove the unreacted monomers, driedand subject to the analysis. and the results analysis of the obtainedpolymer are indicated in table 1.

On Table 2 are reported the characterization data measured on thecompositions obtained by mixing the polymer powders of the Example 1with 1800 ppm of Millad 3988 extruded in a twin-screw extruder Berstorff(L/D=33) under the following operating conditions:

Temperature of the feeding section: 190-210° C.

Melt temperature: 240° C.

Temperature of the die section: 230° C.

Flow rate: 16 Kg/h

Rotational speed: 250 rpm

TABLE 1 Example 1 Component A TEAL/external donor wt/wt 4 TEAL/catalystwt/wt 5 Temperature ° C. 70 Pressure barg 24 Split holdup wt % 40 riserdowncomer wt % 60 H2/C3 riser mol/mol 0.19 (riser)/ 0.076 (downer)C2/(C2 + C3) mol/mol 0.033 (riser)/ 0.005 (downer) MFR g/10 min 20 C2total content wt % 3.2 XS wt % 6.1 Tm ° C. 150 Component B Temperature °C. 80 Pressure MPa 2 Split % 15 C2/C2 + C3 0.8 H2/C2 0.47 C2 = ethyleneC3 = propylene H2 = hydrogen XS = xylene solubles

The properties measured on the samples are collected in Table 2.

TABLE 2 Ex 1 Polymer A MFR g/10′ 20 C2 wt % 3.2 Melting point ° C. 153XS wt % 6 Polymer B % split wt % 15 % C2 copolymer wt % 80 CompositionXSIV Dl/g 1.2 Elongation at break % 420 Izod Impact 23° C. kJ/m2 6 D/BTT ° C. −19.7 Haze (1 mm plaque) % 16.4 XSIV = xylene soluble fractionC2 = ethylene

The invention claimed is:
 1. A propylene composition comprising (percentby weight): A) 60%-95%, of a crystalline propylene copolymer containingfrom 2.0% to 10.0% of ethylene derived units having a melting pointranging from 148° C. to 160° C.; wherein the melting temperature Tm ismeasured by DSC on the as-reactor polymer; and B) 5%-40%, of a copolymerof ethylene containing from 70% to 85%, of ethylene derived units,wherein the copolymer of ethylene has an intrinsic viscosity rangingfrom 0.8 to 3 dl/g.
 2. The composition according to claim 1 whereincomponent A) is a propylene copolymer containing from 3.0% to 6.0% byweight of ethylene derived units and component B) is a copolymer ofethylene containing from 70% to 82%, by weight of ethylene derivedunits.
 3. The composition according to claim 1 wherein the ethylenecontent (C2) and the melting point (Tm) of the component A) meet thefollowing relationship:Tm>C2*−0.56+150.5.
 4. The composition according to claim 1 whereincomponent A) has a melting point ranging from 149° C. to 160° C.
 5. Thecomposition according to claim 1 wherein the relationship between theethylene derived units C2 content and the melting point Tm isTm>C2*−0.56+150.8.
 6. The composition according to claim 1 wherein theintrinsic Viscosity of the fraction (of the overall composition) solublein xylene at room temperature is from 1.2 to 4.5.
 7. The compositionaccording to claim 1 having a haze lower than 25%.
 8. A thermoformedarticle comprising a propylene composition comprising (percent byweight): A) 60%-95%, of a crystalline propylene copolymer containingfrom 2.0% to 10.0% of ethylene derived units having a melting pointranging from 148° C. to 160° C.; wherein the melting temperature Tm ismeasured by DSC on the as-reactor polymer; and B) 5%-40%, of a copolymerof ethylene containing from 70% to 85%, of ethylene derived units,wherein the copolymer of ethylene has an intrinsic viscosity rangingfrom 0.8 to 3 dl/g.